EP2199310B1 - Crosslinkable composition comprising a silane grafted polymer and a latent compound - Google Patents

Crosslinkable composition comprising a silane grafted polymer and a latent compound Download PDF

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Publication number
EP2199310B1
EP2199310B1 EP09177715A EP09177715A EP2199310B1 EP 2199310 B1 EP2199310 B1 EP 2199310B1 EP 09177715 A EP09177715 A EP 09177715A EP 09177715 A EP09177715 A EP 09177715A EP 2199310 B1 EP2199310 B1 EP 2199310B1
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Prior art keywords
composition
cross
latent
composition according
latent compound
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German (de)
French (fr)
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EP2199310A1 (en
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Jérôme Alric
Olivier Pinto
Jean-Michel Marty
Mikael Abeguile
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Nexans SA
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Nexans SA
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
    • C08F230/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
    • C08F230/08—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon
    • C08F230/085—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon the monomer being a polymerisable silane, e.g. (meth)acryloyloxy trialkoxy silanes or vinyl trialkoxysilanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/42—Introducing metal atoms or metal-containing groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
    • C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
    • C08J3/247—Heating methods
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/28—Treatment by wave energy or particle radiation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0025—Crosslinking or vulcanising agents; including accelerators
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
    • C08L23/0892—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms containing monomers with other atoms than carbon, hydrogen or oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L43/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium or a metal; Compositions of derivatives of such polymers
    • C08L43/04—Homopolymers or copolymers of monomers containing silicon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2810/00—Chemical modification of a polymer
    • C08F2810/20—Chemical modification of a polymer leading to a crosslinking, either explicitly or inherently
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2351/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
    • C08J2351/06—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2217—Oxides; Hydroxides of metals of magnesium
    • C08K2003/2224—Magnesium hydroxide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0091—Complexes with metal-heteroatom-bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/56—Organo-metallic compounds, i.e. organic compounds containing a metal-to-carbon bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/56—Organo-metallic compounds, i.e. organic compounds containing a metal-to-carbon bond
    • C08K5/57—Organo-tin compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2312/00—Crosslinking
    • C08L2312/08—Crosslinking by silane

Definitions

  • the present invention relates to a crosslinkable composition comprising an olefin polymer having hydrolyzable silane groups and a latent compound, and to a method of making a crosslinked article from said crosslinkable composition.
  • tin salt crosslinking catalysts such as, for example, dibutyl tin dilaurate (DBTDL).
  • DBTDL dibutyl tin dilaurate
  • EP-1,255,593 proposes to crosslink a polyethylene-based composition using, as crosslinking catalyst, an aromatic sulfonic acid ArSO 3 H or one of its precursors, the precursors being compounds able to convert by hydrolysis to aryl sulfonic acid.
  • aromatic sulfonic acid or its precursors are compounds that are very sensitive to moisture. Thus, their duration of storage and use is severely limited.
  • this catalyst does not guarantee the absence of gel formation during an extrusion step, as a result of premature crosslinking catalysis in an extruder.
  • this catalyst, acid type is not compatible with a so-called "charged" composition, containing in particular basic charges such as metal hydroxides.
  • the object of the present invention is to overcome the drawbacks of the techniques of the prior art by providing in particular a composition based on crosslinkable polyolefin which is insensitive to moisture and ecological, and which can be implemented with any type of polyolefin and at relatively high temperatures.
  • the subject of the present invention is a crosslinkable composition as defined in the subject matter of claim 1.
  • crosslinking catalyst means a catalyst for hydrolysis and condensation of silanol functions.
  • the polymer according to the invention comprises a main chain, comprising a linear or branched sequence of constituent units, located between two end groups at the ends of said main chain.
  • the ends of the main chain do not comprise hydrolyzable silane groups.
  • silane graft polymer The polymer comprising on its main chain hydrolysable silane groups is called in the following description "silane graft polymer”.
  • the term "polymer” as such generally means homopolymer or copolymer.
  • the olefin polymer, or polyolefin, of the invention may therefore be an olefin homo- or co-polymer, and may in particular be a thermoplastic polymer or an elastomer.
  • the olefin polymer is a polymer of ethylene or propylene.
  • ethylene polymers By way of example of ethylene polymers, mention may be made of linear low density polyethylene (LLDPE) and low polyethylene density (LDPE), homo-medium-density polyethylene (MDPE), high-density polyethylene (HDPE), copolymers of ethylene and vinyl acetate (EVA), copolymers of ethylene and butyl acrylate (EBA), methyl acrylate (EMA), 2-hexylethyl acrylate (2HEA), copolymers of ethylene and alpha-olefins such as for example polyethylene-octene (PEO), copolymers of ethylene and propylene (EPR) such as for example terpolymers of ethylene propylene diene monomer (EPDM), and mixtures thereof.
  • LLDPE linear low density polyethylene
  • MDPE homo-medium-density polyethylene
  • HDPE high-density polyethylene
  • EVA ethylene and vinyl acetate
  • EBA methyl acrylate
  • EMA
  • composition of the invention may of course comprise at least one olefin polymer comprising on its main chain hydrolysable silane groups, that is to say that it may comprise a mixture of several olefin polymers having on their main chain of hydrolyzable silane groups.
  • olefin polymers of the invention may or may not comprise other types of polymers, different from the olefin polymers of the invention (i.e. olefin polymer having on its main chain hydrolysable silane groups).
  • crosslinkable composition of the invention comprises other types of polymers other than olefin polymers
  • it may consist of at least 50 parts by weight of olefin polymers of the invention per 100 parts by weight of polymer in said composition, and preferably at least 80 parts by weight of olefin polymers of the invention per 100 parts by weight of polymer in said composition.
  • crosslinkable composition of the invention does not comprise other types of polymers other than olefin polymers having on their main chain hydrolyzable silane groups, it then consists only of one or more olefin polymers of the invention as a polymer in said composition.
  • the hydrolysable silane groups of the polymer of the invention may be alkoxysilane groups and / or carboxysilane groups, preferably alkoxysilane groups.
  • the silane grafted polymer may be obtained by grafting vinyl alkoxysilane onto at least one olefin polymer (or polyolefin) as described above.
  • the silane graft polymer may also be obtained by in situ copolymerization of at least one olefin monomer, preferably at least one ethylene monomer, with a vinyl alkoxysilane. There may be mentioned more particularly copolymers of ethylene and vinyl silane (EVS).
  • EVS ethylene and vinyl silane
  • the content of the latent compound in the composition may be from 50 to 50,000 ppm, preferably from 100 to 5,000 ppm.
  • the abbreviation "ppm” in the present description means “parts per million by weight”.
  • the latent compound or in other words the latent crosslinking catalyst, able to release a crosslinking catalyst under the action of a temperature rise and / or actinic radiation can be defined in several variants.
  • the latent compound is an ionic compound capable of releasing a base, in particular a strong base, as a crosslinking catalyst.
  • This latent compound is then called basic ion generator.
  • the base capable of being released can preferably be a tertiary amine.
  • the latent compound capable of releasing a tertiary amine may be chosen from the ammonium salts of alpha-ketocarboxylic acids; ammonium salts of carboxylic acids carrying an aromatic group, such as, for example, the dimethylbenzyl ammonium salts of alpha-naphthyl acid or the diazabicycloundecene salts of anthracene-9-carboxylic acid; N- (benzophenonymethyl) -tri-N-alkylammonium triphenylalkylborate salts, benzhydrylammonium salts, and trialkylfluorenylammonium iodides, or a mixture thereof.
  • the latent compound is a nonionic compound capable of releasing a base, in particular a strong base, as a crosslinking catalyst.
  • This latent compound is then called basic nonionic generator.
  • the base capable of being released can preferably be a tertiary amine.
  • the tertiary amine may more particularly be an amidine, the latter being especially suitable for use among diazabicyclooctanes, N-alkyl-morpholines, tetramethylguanidines (TMG), diazabicyclononenes (DBN) and diazabicycloundecenes (DBU).
  • the latent compound capable of releasing an amidine may be chosen from diazabicyclononanes and diazabicycloundecanes.
  • latent compounds capable of releasing a tertiary amine may also be mentioned, these latent compounds being, for example, congested tertiary amines.
  • These hindered tertiary amines can be in particular 4- (methylthiobenzoyl) -1-morpholino-ethane, or (4-morpholino-benzol) -1-benzyl-1-dimethylamino propane.
  • composition according to the invention may comprise other compounds well known to those skilled in the art, for example flame retardant fillers or photosensitizers.
  • Another object according to the invention is a method of manufacturing a crosslinked article.
  • the crosslinking step iii of the process of the invention can be conventionally carried out in the presence of humidity and at a controlled temperature.
  • the heating step i is performed at the extrusion head of an extruder, or after extrusion of the composition.
  • the crosslinking step iii of the process of the invention can be conventionally carried out in the presence of humidity and at a controlled temperature.
  • the exposure step ii is performed after extrusion of the composition.
  • the crosslinking step iii of the process of the invention can be conventionally carried out in the presence of humidity and at a controlled temperature.
  • step i can be carried out previously, concomitantly, or after step ii.
  • the crosslinking catalyst required for the crosslinking reaction is produced in situ in the composition.
  • the latent compound can be easily selected according to the temperature and / or the wavelength of the actinic radiation necessary (s) to the release of the crosslinking catalyst.
  • a method for determining the temperature at which the catalyst will be released, or release start temperature can be classically carried out by DSC for the Anglicism Differential Scanning Calorimetry , under a nitrogen atmosphere, with a temperature ramp. 10 ° C / min.
  • This method is based on the principle of the thermal initiation reaction of the polymerization reaction of an epoxide subsequent to the thermal release of the basic crosslinking catalyst from the latent compound.
  • the latent compound is typically solubilized (1% by weight) in a liquid epoxide dilution liquid. This epoxide must be stable at a temperature high enough not to decompose before the latent compound releases the catalyst in situ.
  • liquid epoxide may be the epoxidized polypropylene glycol marketed by Dow under the reference DER 736, this epoxide being stable up to a temperature of 200 ° C.
  • the polymerization of the epoxide catalysed by the crosslinking catalyst from the latent compound is an exothermic reaction. Therefore, the exothermic peak formed during the polymerization reaction through said catalyst is easily identifiable on the DSC analysis curve. The start of release temperature of the crosslinking catalyst is therefore detectable at the base of the exothermic peak formed.
  • the method for determining the wavelength at which the catalyst will be released is conventionally carried out using a UV-Visible absorption spectrophotometer.
  • the latent compound or in other words the latent photoinitiator, is diluted in a solvent inert and transparent in the wavelength range considered (from 185 nm to 800 nm) such as acetonitrile.
  • the solution is subjected to monochromatic radiation by scanning a wavelength range of 185 nm to 800 nm.
  • the intensity of the transmitted light is measured in order to deduce the absorbed light rate as a function of the wavelength (absorption spectrum).
  • the absorption maximum identified in the absorption spectrum obtained makes it possible to ensure that the latent photoinitiator is able to release a crosslinking catalyst at this maximum absorption.
  • the UV-visible light source (s) will be selected according to this absorption maximum.
  • the latent photoinitiator may be selected according to the UV-visible light source (s) available commercially.
  • the composition Prior to step i or ii, the composition may be mixed at a temperature such that the polymer is in the molten state and such that this temperature is lower than the release temperature of the crosslinking catalyst.
  • molten state is meant a state in which the silane graft polymer of step i is in a malleable state. This malleable state, well known to those skilled in the art, can be conventionally achieved when the polymer in question is heated to a temperature equal to or greater than its melting temperature when this polymer is thermoplastic.
  • the choice of the compound can be made according to the polymer operating temperature so as not to thermally release the crosslinking catalyst when the silane graft polymer is in the molten state.
  • this step can be carried out in an extruder.
  • silane graft polymer of the composition according to the present invention can be prepared by methods well known to those skilled in the art under the names MONOSIL ® process and SIOPLAS ® process.
  • the composition according to the invention is obtained from a mixture M1 comprising reagents capable of producing silane-grafted polymer and the latent compound according to the invention.
  • This mixture M1 is heated to a temperature sufficient to obtain a silane grafted polymer (grafting step), and therefore a composition according to the invention.
  • the following steps are those described according to the method of the invention.
  • the composition according to the invention is obtained from a mixture M2 comprising reagents capable of producing silane-grafted polymer.
  • This mixture M2 is heated to a temperature sufficient to obtain a silane grafted polymer (grafting step).
  • the latent compound according to the invention is incorporated in the mixture M2, and a composition is thus obtained according to the invention.
  • the following steps are those described according to the method of the invention.
  • Another subject of the invention relates to a crosslinked article obtained from the composition according to the invention or obtained from the process according to the invention.
  • compositions 1 to 3 the constituents of which are mentioned in Table 1 below, are prepared.
  • ⁇ b> ⁇ u> Table 1 ⁇ / u> ⁇ /b> Composition 1 2 3 EVS (% by weight) 44 - - LLDPE-grafted silane (% by weight) - 36 37 Flame retardant load (% by weight) 52 60 61 Masterbatch (% by weight) 4 4 2 - - - DBTm (ppm) - - 75 - - - PBL (ppm) 2000 2000 - Photo-sensitizer (ppm) 2000 2000 -
  • compositions 1 and 2 are furthermore lower than the release temperature of the crosslinking catalyst of the latent compounds (compositions 1 and 2). More particularly, the temperature profile of the extruder is as follows: 120 ° C - 150 ° C - 160 ° C, with an extrusion head temperature of 170 ° C. At 170 ° C., the thermal stability of the latent compounds PAG and PBL is sufficient not to release their respective crosslinking catalyst during the mixing of the compositions in the extruder.
  • the respective amounts of masterbatch in compositions 1 to 3 are detailed in Table 1.
  • the contents of latent compounds, dibutyltin salt and photosensitizer for compositions 1 to 3 are also shown in Table 1.
  • the extrusion step of the various compositions 1 to 3 is carried out at a speed of 10 m / min, by depositing a thickness of 300 .mu.m of said extruded composition around a copper conductor wire of 0.85 mm 2 of cross section.
  • the isolated yarn obtained is immediately irradiated with UV radiation (first UV treatment), with a wavelength of between 150 and 550 nm, at room temperature, using an HP6 type furnace sold by the company FUSION UV SYSTEMS equipped with a medium-pressure mercury vapor lamp type "D" with a power of 200 W / cm and a rear reflector module.
  • first UV treatment UV radiation
  • a UV post-treatment step may be necessary. This can be performed on the insulated wire at room temperature subsequent to the extrusion step.
  • the post-treatment UV consists in passing the insulated wire 10 times at 10m / min in the UV oven.
  • compositions having undergone a first UV treatment, and possibly a UV post-treatment are indicated in Table 2 below.
  • the method chosen is that of the measurement of the hot creep under load.
  • the standard NF EN 60811-2-1 describes the measurement of the hot flow of a material under load.
  • the corresponding test is commonly referred to as the Anglicism Hot Set Test.
  • Table 2 shows the results of hot flowing obtained on the samples considered. ⁇ b> ⁇ u> Table 2 ⁇ / u> ⁇ /b> Composition UV treatment (first UV treatment) UV post-treatment Crosslinking conditions Hot creep Lengthening under load (%) Remanence (%) 1 YES YES SELF-CURE 95 25 YES YES SAUNA 75 15 2 YES YES SELF-CURE 40 5 YES YES SAUNA 30 0 3 NO NO SELF-CURE FAILURE FAILURE
  • composition 1 EVS + Mg (OH) 2 + PBL
  • composition 2 LLDPE-grafted silane + Mg (OH) 2 + PBL
  • the UV post-treatment also makes it possible to improve the crosslinking effectively.
  • the charged compositions 1 and 2 after UV post-treatment, are self-crosslinking, unlike the charged composition 3 (compared to the charged composition 2) where the self-crosslinking is not done after 48 hours, or even after several dozens of days.
  • PAG PBL latent crosslinking catalyst
  • DBTm tin salt

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Graft Or Block Polymers (AREA)

Abstract

Crosslinkable composition (I) comprises: an olefin polymer comprising hydrolysable silane groups on its main chain; and a latent compound capable of releasing a crosslinking catalyst under the action of elevated temperature and/or actinic radiation, where the crosslinking catalyst is a catalyst for hydrolysis and condensation of silanol groups. Independent claims are included for fabricating a crosslinked article comprising: (a) heating the composition (I) for releasing the crosslinking catalyst from latent compound and (b) crosslinking the composition obtained in step (a); or (a1) exposing the composition (I) to an actinic radiation to release the crosslinking catalyst from latent compound and (b1) crosslinking the composition obtained in step (a1).

Description

La présente invention se rapporte à une composition réticulable comprenant un polymère d'oléfine comportant des groupements silane hydrolysables et un composé latent, ainsi qu'à un procédé de fabrication d'un article réticulé à partir de ladite composition réticulable.The present invention relates to a crosslinkable composition comprising an olefin polymer having hydrolyzable silane groups and a latent compound, and to a method of making a crosslinked article from said crosslinkable composition.

Elle s'applique typiquement, mais non exclusivement, à la fabrication d'articles réticulés du type couche isolante pour câble électrique et/ou optique, ou du type tube ou tuyau de canalisation pour le transport d'eau, de pétrole ou de gaz.It typically, but not exclusively, applies to the manufacture of cross-linked articles of the insulating layer type for electrical and / or optical cable, or of the tube or pipeline pipe type for transporting water, oil or gas.

Les techniques actuelles pour réticuler des compositions polymères à base d'une polyoléfine avec des groupements silane hydrolysables utilisent des catalyseurs de réticulation du type sel d'étain comme par exemple le dibutyle étain dilaurate (DBTDL). Toutefois, ces catalyseurs sont néfastes pour l'environnement et vont devoir être remplacés par des catalyseurs moins polluants selon les réglementations à venir.Current techniques for crosslinking polyolefin-based polymer compositions with hydrolysable silane groups use tin salt crosslinking catalysts such as, for example, dibutyl tin dilaurate (DBTDL). However, these catalysts are harmful to the environment and will have to be replaced by less polluting catalysts according to future regulations.

Pour pallier cet inconvénient, le document EP-1 256 593 propose de réticuler une composition à base de polyéthylène en utilisant, comme catalyseur de réticulation, un acide sulfonique aromatique ArSO3H ou un de ses précurseurs, les précurseurs étant des composés aptes à se convertir par hydrolyse en acide aryle sulfonique. Toutefois, l'acide sulfonique aromatique ou ses précurseurs sont des composés très sensibles à l'humidité. Ainsi, leur durée de stockage et d'utilisation est fortement limitée. De plus, ce catalyseur ne garantit pas l'absence de formation de gel lors d'une étape d'extrusion, conséquente à une catalyse de réticulation prématurée dans une extrudeuse. Enfin, ce catalyseur, de type acide, n'est pas compatible avec une composition dite « chargée », contenant notamment des charges basiques telles que des hydroxydes métalliques.To overcome this drawback, the document EP-1,255,593 proposes to crosslink a polyethylene-based composition using, as crosslinking catalyst, an aromatic sulfonic acid ArSO 3 H or one of its precursors, the precursors being compounds able to convert by hydrolysis to aryl sulfonic acid. However, aromatic sulfonic acid or its precursors are compounds that are very sensitive to moisture. Thus, their duration of storage and use is severely limited. In addition, this catalyst does not guarantee the absence of gel formation during an extrusion step, as a result of premature crosslinking catalysis in an extruder. Finally, this catalyst, acid type, is not compatible with a so-called "charged" composition, containing in particular basic charges such as metal hydroxides.

Le but de la présente invention est de pallier les inconvénients des techniques de l'art antérieur en proposant notamment une composition à base de polyoléfine réticulable qui est insensible à l'humidité et écologique, et qui peut être mise en oeuvre avec n'importe quel type de polyoléfine et à des températures relativement élevées.The object of the present invention is to overcome the drawbacks of the techniques of the prior art by providing in particular a composition based on crosslinkable polyolefin which is insensitive to moisture and ecological, and which can be implemented with any type of polyolefin and at relatively high temperatures.

La présente invention a pour objet une composition réticulable telle que définie dans l'objet de la revendication 1.The subject of the present invention is a crosslinkable composition as defined in the subject matter of claim 1.

On entend par « catalyseur de réticulation » un catalyseur d'hydrolyse et de condensation de fonctions silanol.The term "crosslinking catalyst" means a catalyst for hydrolysis and condensation of silanol functions.

Le polymère selon l'invention comprend une chaîne principale, comportant une séquence linéaire ou ramifiée d'unités constitutives, située entre deux groupements terminaux aux extrémités de ladite chaîne principale. De préférence, les extrémités de la chaîne principale ne comportent pas de groupements silane hydrolysables.The polymer according to the invention comprises a main chain, comprising a linear or branched sequence of constituent units, located between two end groups at the ends of said main chain. Preferably, the ends of the main chain do not comprise hydrolyzable silane groups.

Le polymère comportant sur sa chaîne principale des groupements silane hydrolysables est appelé dans la suite de la description « polymère greffé silane ».The polymer comprising on its main chain hydrolysable silane groups is called in the following description "silane graft polymer".

Le terme « polymère » en tant que tel signifie de façon générale homopolymère ou copolymère. Le polymère d'oléfine, ou polyoléfine, de l'invention peut donc être un homo- ou co-polymère d'oléfine, et peut être notamment un polymère thermoplastique ou un élastomère. De préférence, le polymère d'oléfine est un polymère d'éthylène ou de propylène.The term "polymer" as such generally means homopolymer or copolymer. The olefin polymer, or polyolefin, of the invention may therefore be an olefin homo- or co-polymer, and may in particular be a thermoplastic polymer or an elastomer. Preferably, the olefin polymer is a polymer of ethylene or propylene.

A titre d'exemple de polymères d'éthylène, on peut citer le polyéthylène linéaire basse densité (LLDPE), le polyéthylène basse densité (LDPE), l'homo-polyéthylène moyenne densité (MDPE), le polyéthylène haute densité (HDPE), les copolymères d'éthylène et d'acétate de vinyle (EVA), les copolymères d'éthylène et d'acrylate de butyle (EBA), d'acrylate de méthyle (EMA), de 2-hexyléthyl acrylate (2HEA), les copolymères d'éthylène et d'alpha-oléfines tels que par exemple les polyéthylène-octène (PEO), les copolymères d'éthylène et de propylène (EPR) tels que par exemple les terpolymères d'éthylène propylène diène monomère (EPDM), et leurs mélanges.By way of example of ethylene polymers, mention may be made of linear low density polyethylene (LLDPE) and low polyethylene density (LDPE), homo-medium-density polyethylene (MDPE), high-density polyethylene (HDPE), copolymers of ethylene and vinyl acetate (EVA), copolymers of ethylene and butyl acrylate (EBA), methyl acrylate (EMA), 2-hexylethyl acrylate (2HEA), copolymers of ethylene and alpha-olefins such as for example polyethylene-octene (PEO), copolymers of ethylene and propylene (EPR) such as for example terpolymers of ethylene propylene diene monomer (EPDM), and mixtures thereof.

La composition de l'invention peut bien entendu comprendre au moins un polymère d'oléfine comportant sur sa chaîne principale des groupements silane hydrolysables, c'est-à-dire qu'elle peut comprendre un mélange de plusieurs polymères d'oléfine comportant sur leur chaîne principale des groupements silane hydrolysables.The composition of the invention may of course comprise at least one olefin polymer comprising on its main chain hydrolysable silane groups, that is to say that it may comprise a mixture of several olefin polymers having on their main chain of hydrolyzable silane groups.

En outre, elle peut comprendre ou non d'autres types de polymères, différents des polymères d'oléfine de l'invention (i.e. polymère d'oléfine comportant sur sa chaîne principale des groupements silane hydrolysables).In addition, it may or may not comprise other types of polymers, different from the olefin polymers of the invention (i.e. olefin polymer having on its main chain hydrolysable silane groups).

Lorsque la composition réticulable de l'invention comprend d'autres types de polymères différents des polymères d'oléfine, elle peut se composer d'au moins 50 parties en poids de polymères d'oléfine de l'invention pour 100 parties en poids de polymère dans ladite composition, et de préférence d'au moins 80 parties en poids de polymères d'oléfine de l'invention pour 100 parties en poids de polymère dans ladite composition.When the crosslinkable composition of the invention comprises other types of polymers other than olefin polymers, it may consist of at least 50 parts by weight of olefin polymers of the invention per 100 parts by weight of polymer in said composition, and preferably at least 80 parts by weight of olefin polymers of the invention per 100 parts by weight of polymer in said composition.

Lorsque la composition réticulable de l'invention ne comprend pas d'autres types de polymères différents des polymères d'oléfine comportant sur leur chaîne principale des groupements silane hydrolysables, elle se compose alors uniquement d'un ou de plusieurs polymères d'oléfine de l'invention en tant que polymère dans ladite composition.When the crosslinkable composition of the invention does not comprise other types of polymers other than olefin polymers having on their main chain hydrolyzable silane groups, it then consists only of one or more olefin polymers of the invention as a polymer in said composition.

Les groupements silane hydrolysables du polymère de l'invention peuvent être des groupements alcoxysilanes et/ou des groupements carboxysilanes, de préférence des groupements alcoxysilanes.The hydrolysable silane groups of the polymer of the invention may be alkoxysilane groups and / or carboxysilane groups, preferably alkoxysilane groups.

A titre d'exemple, le polymère greffé silane peut être obtenu par greffage de vinyle alcoxysilane sur au moins un polymère d'oléfine (ou polyoléfine) tel que décrit ci-avant.By way of example, the silane grafted polymer may be obtained by grafting vinyl alkoxysilane onto at least one olefin polymer (or polyolefin) as described above.

Le polymère greffé silane peut également être obtenu par copolymérisation in situ d'au moins un monomère d'oléfine, de préférence au moins un monomère d'éthylène, avec un vinyle alcoxysilane. On peut citer plus particulièrement les copolymères d'éthylène et de vinyl silane (EVS).The silane graft polymer may also be obtained by in situ copolymerization of at least one olefin monomer, preferably at least one ethylene monomer, with a vinyl alkoxysilane. There may be mentioned more particularly copolymers of ethylene and vinyl silane (EVS).

La teneur du composé latent dans la composition peut être de 50 à 50000 ppm, de préférence de 100 à 5000 ppm. L'abréviation « ppm » dans la présente description signifie « parties par million massiques».The content of the latent compound in the composition may be from 50 to 50,000 ppm, preferably from 100 to 5,000 ppm. The abbreviation "ppm" in the present description means "parts per million by weight".

Le composé latent, ou en d'autres termes le catalyseur de réticulation latent, apte à libérer un catalyseur de réticulation sous l'action d'une élévation de température et/ou d'un rayonnement actinique peut être défini selon plusieurs variantes.The latent compound, or in other words the latent crosslinking catalyst, able to release a crosslinking catalyst under the action of a temperature rise and / or actinic radiation can be defined in several variants.

Selon une première variante, le composé latent est un composé ionique apte à libérer une base, notamment une base forte, comme catalyseur de réticulation. Ce composé latent est alors appelé générateur ionique de base.According to a first variant, the latent compound is an ionic compound capable of releasing a base, in particular a strong base, as a crosslinking catalyst. This latent compound is then called basic ion generator.

La base apte à être libérée peut être de préférence une amine tertiaire. Dans ce cas, le composé latent apte à libérer une amine tertiaire peut être choisi parmi les sels d'ammonium d'acides alpha-cétocarboxyliques ; les sels d'ammonium d'acides carboxyliques portant un groupement aromatique tels que par exemple les sels de dimethylbenzyl ammonium d'acide alpha-naphtyle ou les sels de diazabicycloundecene d'acide anthracene-9-carboxylique ; les sels de N-(benzophenonymethyl)-tri-N-alkyl-ammonium triphenylalkyl-borates, les sels de benzhydrylammonium, et les iodures de trialkylfluorenyl ammonium, ou un de leurs mélanges.The base capable of being released can preferably be a tertiary amine. In this case, the latent compound capable of releasing a tertiary amine may be chosen from the ammonium salts of alpha-ketocarboxylic acids; ammonium salts of carboxylic acids carrying an aromatic group, such as, for example, the dimethylbenzyl ammonium salts of alpha-naphthyl acid or the diazabicycloundecene salts of anthracene-9-carboxylic acid; N- (benzophenonymethyl) -tri-N-alkylammonium triphenylalkylborate salts, benzhydrylammonium salts, and trialkylfluorenylammonium iodides, or a mixture thereof.

Selon une deuxième variante, le composé latent est un composé non ionique apte à libérer une base, notamment une base forte, comme catalyseur de réticulation. Ce composé latent est alors appelé générateur non ionique de base.According to a second variant, the latent compound is a nonionic compound capable of releasing a base, in particular a strong base, as a crosslinking catalyst. This latent compound is then called basic nonionic generator.

La base apte à être libérée peut être de préférence une amine tertiaire.The base capable of being released can preferably be a tertiary amine.

L'amine tertiaire peut être plus particulièrement une amidine, cette dernière pouvant notamment être choisie parmi les diazabicyclooctanes, les N-alkyl-morpholines, les tétramethylguanidines (TMG), les diazabicyclononenes (DBN), et les diazabicycloundecenes (DBU). Dans ce cas, le composé latent apte à libérer une amidine peut être choisi parmi les diazabicyclononanes et les diazabicycloundecanes.The tertiary amine may more particularly be an amidine, the latter being especially suitable for use among diazabicyclooctanes, N-alkyl-morpholines, tetramethylguanidines (TMG), diazabicyclononenes (DBN) and diazabicycloundecenes (DBU). In this case, the latent compound capable of releasing an amidine may be chosen from diazabicyclononanes and diazabicycloundecanes.

On peut également citer d'autres composés latents aptes à libérer une amine tertiaire, ces composés latents étant par exemple des amines tertiaires encombrées. Ces amines tertiaires encombrées peuvent être notamment le 4-(methylthiobenzoyl)-1-morpholino-ethane, ou le (4-morpholino-benzol)-1-benzyl-1-dimethyl-amino propane.Other latent compounds capable of releasing a tertiary amine may also be mentioned, these latent compounds being, for example, congested tertiary amines. These hindered tertiary amines can be in particular 4- (methylthiobenzoyl) -1-morpholino-ethane, or (4-morpholino-benzol) -1-benzyl-1-dimethylamino propane.

Entre les générateurs ioniques ou non ioniques base, ce sont les générateurs non ioniques de base qui sont préférés puisque ils présentent une meilleure compatibilité physicochimique avec le polymère greffé silane de l'invention comme notamment une meilleure solubilité dans ledit polymère.Between basic ionic and nonionic generators, it is the basic nonionic generators which are preferred since they exhibit a better physicochemical compatibility with the silane graft polymer of the invention, such as in particular a better solubility in said polymer.

La composition selon l'invention peut comprendre d'autres composés bien connus de l'homme du métier comme par exemple des charges ignifugeantes ou des photosensibilisateurs.The composition according to the invention may comprise other compounds well known to those skilled in the art, for example flame retardant fillers or photosensitizers.

Un autre objet selon l'invention est un procédé de fabrication d'un article réticulé.Another object according to the invention is a method of manufacturing a crosslinked article.

Dans une première variante, le procédé de fabrication d'un article réticulé comprend les étapes consistant à :

  • i. chauffer la composition telle que définie ci-avant afin de libérer le catalyseur de réticulation du composé latent, et
  • iii. réticuler la composition obtenue à l'étape i.
In a first variant, the method of manufacturing a crosslinked article comprises the steps of:
  • i. heating the composition as defined above in order to release the crosslinking catalyst of the latent compound, and
  • iii. crosslinking the composition obtained in step i.

L'étape de réticulation iii du procédé de l'invention peut être classiquement réalisée en présence d'humidité et à température contrôlée.The crosslinking step iii of the process of the invention can be conventionally carried out in the presence of humidity and at a controlled temperature.

Dans un mode de réalisation particulier, l'étape de chauffage i est réalisée au niveau de la tête d'extrusion d'une extrudeuse, ou après extrusion de la composition.In a particular embodiment, the heating step i is performed at the extrusion head of an extruder, or after extrusion of the composition.

Dans une deuxième variante, le procédé de fabrication d'un article réticulé comprend les étapes consistant à :

  • ii. exposer la composition telle que définie ci-avant à un rayonnement actinique afin de libérer le catalyseur de réticulation du composé latent, le rayonnement actinique ayant de préférence une longueur d'onde allant de 150 nm à 800 nm, de préférence une longueur d'onde allant de 185 nm à 800 nm (UV-visible) et encore plus préférentiellement une longueur d'onde allant de 185 nm à 400 nm (UV), et
  • iii. réticuler la composition obtenue à l'étape ii.
In a second variant, the method of manufacturing a crosslinked article comprises the steps of:
  • ii. exposing the composition as defined above to actinic radiation in order to release the crosslinking catalyst from the latent compound, the actinic radiation preferably having a wavelength ranging from 150 nm to 800 nm, preferably a wavelength ranging from 185 nm to 800 nm (UV-visible) and even more preferably a wavelength ranging from 185 nm to 400 nm (UV), and
  • iii. crosslinking the composition obtained in step ii.

L'étape de réticulation iii du procédé de l'invention peut être classiquement réalisée en présence humidité et à température contrôlée.The crosslinking step iii of the process of the invention can be conventionally carried out in the presence of humidity and at a controlled temperature.

Dans un mode de réalisation particulier, l'étape d'exposition ii est réalisée après extrusion de la composition.In a particular embodiment, the exposure step ii is performed after extrusion of the composition.

Dans une troisième variante, le procédé de fabrication d'un article réticulé comprend, dans un ordre indifférent les étapes i et ii telles que décrites ci-avant, et l'étape consistant à :

  • iii. réticuler la composition obtenue à l'étape précédente.
In a third variant, the process for manufacturing a crosslinked article comprises, in any order, steps i and ii as described above, and the step of:
  • iii. crosslink the composition obtained in the previous step.

L'étape de réticulation iii du procédé de l'invention peut être classiquement réalisée en présence humidité et à température contrôlée.The crosslinking step iii of the process of the invention can be conventionally carried out in the presence of humidity and at a controlled temperature.

On entend par les termes « ordre indifférent », le fait que l'étape i peut être réalisée antérieurement, concomitamment, ou postérieurement à l'étape ii.By the terms "indifferent order" is meant the fact that step i can be carried out previously, concomitantly, or after step ii.

Ainsi, dans le procédé de l'invention quelque soit la variante du procédé prise en compte, le catalyseur de réticulation nécessaire à la réaction de réticulation est produit in situ, dans la composition.Thus, in the process of the invention, whatever the variant of the process taken into account, the crosslinking catalyst required for the crosslinking reaction is produced in situ in the composition.

Le composé latent pourra être facilement choisi selon la température et/ou la longueur d'onde du rayonnement actinique nécessaire(s) à la libération du catalyseur de réticulation.The latent compound can be easily selected according to the temperature and / or the wavelength of the actinic radiation necessary (s) to the release of the crosslinking catalyst.

Une méthode de détermination de la température à laquelle le catalyseur va se libérer, ou température de début de libération, peut être classiquement réalisée par DSC pour l'anglicisme « Differential Scanning Calorimetry », sous une atmosphère d'azote, avec une rampe de température de 10°C/min. Cette méthode est basée sur le principe de la réaction d'amorçage thermique de la réaction de polymérisation d'un époxyde consécutive à la libération thermique du catalyseur de réticulation basique provenant du composé latent. Le composé latent est typiquement solubilisé (1 % en poids) dans un liquide de dilution du type époxyde liquide. Cet époxyde doit être stable à une température suffisamment élevée pour ne pas se décomposer avant que le composé latent ne libère in situ le catalyseur. Un exemple d'époxyde liquide peut être le polypropylène glycol époxydé commercialisé par la société DOW sous la référence DER 736, cet époxyde étant stable jusqu'à une température de 200°C. La polymérisation de l'époxyde catalysée par le catalyseur de réticulation provenant du composé latent est une réaction exothermique. Par conséquent, le pic exothermique formé lors de la réaction de polymérisation grâce audit catalyseur est facilement identifiable sur la courbe d'analyse DSC. La température de début de libération du catalyseur de réticulation est donc repérable à la base du pic exothermique formé.A method for determining the temperature at which the catalyst will be released, or release start temperature, can be classically carried out by DSC for the Anglicism Differential Scanning Calorimetry , under a nitrogen atmosphere, with a temperature ramp. 10 ° C / min. This method is based on the principle of the thermal initiation reaction of the polymerization reaction of an epoxide subsequent to the thermal release of the basic crosslinking catalyst from the latent compound. The latent compound is typically solubilized (1% by weight) in a liquid epoxide dilution liquid. This epoxide must be stable at a temperature high enough not to decompose before the latent compound releases the catalyst in situ. An example of a liquid epoxide may be the epoxidized polypropylene glycol marketed by Dow under the reference DER 736, this epoxide being stable up to a temperature of 200 ° C. The polymerization of the epoxide catalysed by the crosslinking catalyst from the latent compound is an exothermic reaction. Therefore, the exothermic peak formed during the polymerization reaction through said catalyst is easily identifiable on the DSC analysis curve. The start of release temperature of the crosslinking catalyst is therefore detectable at the base of the exothermic peak formed.

La méthode de détermination de la longueur d'onde à laquelle le catalyseur va se libérer est classiquement réalisée à l'aide d'un spectrophotomètre d'absorption UV - Visible. Le composé latent, ou en d'autres termes le photoamorceur latent, est dilué dans un solvant inerte et transparent dans le domaine de longueur d'onde considéré (de 185 nm à 800 nm) tel que l'acétonitrile. La solution est soumise à un rayonnement monochromatique en balayant un domaine de longueur d'onde de 185 nm à 800 nm. L'intensité de la lumière transmise est mesurée de façon à déduire le taux de lumière absorbée en fonction de la longueur d'onde (spectre d'absorption). Le maximum d'absorption identifié dans le spectre d'absorption obtenu permet de s'assurer que le photoamorceur latent est apte à libérer un catalyseur de réticulation à cette absorption maximum. Ainsi, la ou les source(s) lumineuse(s) UV-visible seront sélectionnées en fonction de ce maximum d'absorption. Inversement, le photoamorceur latent pourra être sélectionné en fonction du ou des source(s) lumineuse(s) UV-visible disponible(s) commercialement.The method for determining the wavelength at which the catalyst will be released is conventionally carried out using a UV-Visible absorption spectrophotometer. The latent compound, or in other words the latent photoinitiator, is diluted in a solvent inert and transparent in the wavelength range considered (from 185 nm to 800 nm) such as acetonitrile. The solution is subjected to monochromatic radiation by scanning a wavelength range of 185 nm to 800 nm. The intensity of the transmitted light is measured in order to deduce the absorbed light rate as a function of the wavelength (absorption spectrum). The absorption maximum identified in the absorption spectrum obtained makes it possible to ensure that the latent photoinitiator is able to release a crosslinking catalyst at this maximum absorption. Thus, the UV-visible light source (s) will be selected according to this absorption maximum. Conversely, the latent photoinitiator may be selected according to the UV-visible light source (s) available commercially.

Préalablement à l'étape i ou ii, la composition peut être mélangée à une température telle que le polymère soit à l'état fondu et telle que cette température soit inférieure à la température de libération du catalyseur de réticulation. On entend par « état fondu » un état dans lequel le polymère greffé silane de l'étape i est dans un état malléable. Cet état malléable, bien connu de l'homme du métier, peut être classiquement atteint lorsque le polymère en question est chauffé à une température environ égale ou supérieure à sa température de fusion lorsque ce polymère est thermoplastique.Prior to step i or ii, the composition may be mixed at a temperature such that the polymer is in the molten state and such that this temperature is lower than the release temperature of the crosslinking catalyst. By "molten state" is meant a state in which the silane graft polymer of step i is in a malleable state. This malleable state, well known to those skilled in the art, can be conventionally achieved when the polymer in question is heated to a temperature equal to or greater than its melting temperature when this polymer is thermoplastic.

En outre, le choix du composé peut être fait en fonction de la température de mise en oeuvre du polymère afin de ne pas libérer thermiquement le catalyseur de réticulation lorsque le polymère greffé silane est à l'état fondu.In addition, the choice of the compound can be made according to the polymer operating temperature so as not to thermally release the crosslinking catalyst when the silane graft polymer is in the molten state.

Lorsque le procédé comprend ladite étape préalable de mélange telle que mentionnée ci-avant, cette étape peut être réalisée dans une extrudeuse.When the process comprises said preliminary mixing step as mentioned above, this step can be carried out in an extruder.

Le polymère greffé silane de la composition selon la présente invention peut être préparé par des procédés bien connus de l'homme du métier sous les noms de procédé MONOSIL® et de procédé SIOPLAS®.The silane graft polymer of the composition according to the present invention can be prepared by methods well known to those skilled in the art under the names MONOSIL ® process and SIOPLAS ® process.

Dans le cas du procédé MONOSIL®, la composition selon l'invention est obtenue à partir d'un mélange M1 comprenant les réactifs permettant d'obtenir le polymère greffé silane ainsi que le composé latent selon l'invention. Ce mélange M1 est chauffé à une température suffisante pour obtenir un polymère greffé silane (étape de greffage), et donc une composition conformément à l'invention. Les étapes suivantes sont celles décrites selon le procédé de l'invention.In the case of method MONOSIL ®, the composition according to the invention is obtained from a mixture M1 comprising reagents capable of producing silane-grafted polymer and the latent compound according to the invention. This mixture M1 is heated to a temperature sufficient to obtain a silane grafted polymer (grafting step), and therefore a composition according to the invention. The following steps are those described according to the method of the invention.

Dans le cas du procédé SIOPLAS®, la composition selon l'invention est obtenue à partir d'un mélange M2 comprenant les réactifs permettant d'obtenir le polymère greffé silane. Ce mélange M2 est chauffé à une température suffisante pour obtenir un polymère greffé silane (étape de greffage). Puis, on incorpore dans le mélange M2 le composé latent selon l'invention, et l'on obtient ainsi une composition conformément à l'invention. Les étapes suivantes sont celles décrites selon le procédé de l'invention.In the case of method SIOPLAS ®, the composition according to the invention is obtained from a mixture M2 comprising reagents capable of producing silane-grafted polymer. This mixture M2 is heated to a temperature sufficient to obtain a silane grafted polymer (grafting step). Subsequently, the latent compound according to the invention is incorporated in the mixture M2, and a composition is thus obtained according to the invention. The following steps are those described according to the method of the invention.

Un autre objet de l'invention concerne un article réticulé obtenu à partir de la composition selon l'invention ou obtenu à partir du procédé selon l'invention.Another subject of the invention relates to a crosslinked article obtained from the composition according to the invention or obtained from the process according to the invention.

Cet article peut être sous forme :

  • d'une couche isolante pour câble électrique et/ou optique, ou
  • d'un tube ou d'un tuyau, comme par exemple des canalisations pour le chauffage hydronique, des conduites d'alimentation d'eau, des canalisations pour le transport du gaz ou de pétrole pour les installations off-shore, ...etc.
This article can be in the form:
  • an insulating layer for electrical and / or optical cable, or
  • a pipe or pipe, such as pipes for hydronic heating, water supply pipes, pipelines for the transport of gas or oil for off-shore installations, etc. .

D'autres caractéristiques et avantages de la présente invention apparaîtront à la lumière des exemples qui vont suivre, lesdits exemples étant donnés à titre illustratif et nullement limitatif.Other features and advantages of the present invention will emerge in the light of the examples which follow, said examples being given by way of illustration and in no way limiting.

ExemplesExamples Préparation des compositionsPreparation of compositions

On prépare les compositions 1 à 3 dont les constituants sont mentionnés dans le tableau 1 ci-dessous. Tableau 1 Composition 1 2 3 EVS (% en poids) 44 - - LLDPE-greffé silane (% en poids) - 36 37 Charge ignifugeante (% en poids) 52 60 61 Mélange-maître (% en poids) 4 4 2 - - - DBTm (ppm) - - 75 - - - PBL (ppm) 2000 2000 - Photo-sensibilisateur (ppm) 2000 2000 - Compositions 1 to 3, the constituents of which are mentioned in Table 1 below, are prepared. <b><u> Table 1 </ u></b> Composition 1 2 3 EVS (% by weight) 44 - - LLDPE-grafted silane (% by weight) - 36 37 Flame retardant load (% by weight) 52 60 61 Masterbatch (% by weight) 4 4 2 - - - DBTm (ppm) - - 75 - - - PBL (ppm) 2000 2000 - Photo-sensitizer (ppm) 2000 2000 -

L'origine des constituants mentionnés dans le tableau 1 est la suivante :

  • EVS correspond au copolymère d'éthylène-vinyl-silane commercialisé par la société Borealis sous le nom de LE4421.
  • LLDPE-greffé silane correspond au polyéthylene basse densité linéaire commercialisé par la société Exxon Mobil Chemical sous le nom de LL4004 greffé avec de du vinyl-trimétoxy-silane en présence de dicumyle peroxyde selon le protocole décrit dans le document brevet FR-2 030 899 .
  • Charge ignifugeante correspond au Mg(OH)2 commercialisé par la société Albemarle sous la référence Magnifin H10.
  • DBTm correspond au bis-(2-éthyle hexyle mercapto acétate) de dibutyle étain commercialisé par la société Crompton sous la référence MARK 17M.
  • PBL est un générateur non ionique de base apte à libérer une amine tertiaire, commercialisé par la société Ciba sous la référence CGI 1193.
  • Photosensibilisateur correspond à l'isopropyl thioxanthone commercialisé par la société Rahn sous la référence GENOCURE-ITX.
The origin of the constituents mentioned in Table 1 is as follows:
  • EVS corresponds to the ethylene-vinyl-silane copolymer marketed by Borealis under the name LE4421.
  • Silane-grafted LLDPE is the linear low density polyethylene marketed by Exxon Mobil Chemical under the name LL4004 grafted with vinyltrimethoxysilane in the presence of dicumyl peroxide according to the protocol described in the patent document. FR-2,030,899 .
  • Flame retardant charge corresponds to Mg (OH) 2 marketed by Albemarle under the reference Magnifin H10.
  • DBTm corresponds to the bis (2-ethyl hexyl mercapto acetate) dibutyl tin marketed by Crompton under the reference MARK 17M.
  • PBL is a basic nonionic generator capable of releasing a tertiary amine, marketed by Ciba under the reference CGI 1193.
  • Photosensitizer is the isopropyl thioxanthone marketed by Rahn under the reference GENOCURE-ITX.

Tout d'abord, différents mélange-maîtres sont préparés comme suit :

  • lorsque le composé latent est le PBL, on incorpore 5 % en poids du composé latent ainsi que 5 % en poids du photosensibilisateur, d'une part, dans une matrice EVS lorsqu'il s'agit de réticuler un EVS chargé (composition 1), et d'autre part, dans une matrice LLDPE (non greffé silane) lorsqu'il s'agit de réticuler un LLDPE greffé silane chargé (composition 2).
  • lorsque le catalyseur est du type sel de dibutyle étain, on incorpore 0,36 partie en poids dudit catalyseur dans une matrice de LLDPE (non greffé silane) lorsqu'il s'agit de réticuler du LLDPE-greffé silane chargé (Composition 3).
First, different masterbatch are prepared as follows:
  • when the latent compound is PBL, 5% by weight of the latent compound and 5% by weight of the photosensitizer are incorporated firstly into an EVS matrix when it is a question of crosslinking a charged EVS (composition 1) and, on the other hand, in an LLDPE (ungrafted silane) matrix when it is a question of cross-linking a charged silane grafted LLDPE (composition 2).
  • when the catalyst is of the dibutyl tin salt type, 0.36 parts by weight of said catalyst are incorporated in an LLDPE (non-grafted silane) matrix when it is a question of cross-linking of charged silane-grafted LLDPE (Composition 3).

Ensuite, ces différents mélange-maîtres sont ajoutés par la trémie d'une extrudeuse dans un mélange d'EVS ou de LLDPE greffé-silane conformément aux compositions référencées dans le tableau 1. Le profil de température de l'extrudeuse permet au mélange de polymères obtenu de se trouver à l'état fondu. La température maximale du profil est en outre inférieure à la température de libération du catalyseur de réticulation des composés latents (compositions 1 et 2). Plus particulièrement, le profil de température de l'extrudeuse est le suivant : 120°C - 150°C - 160°C, avec une température en tête d'extrusion de 170°C. A 170°C, la stabilité thermique des composés latents PAG et PBL est suffisante pour ne pas libérer leur catalyseur de réticulation respectif au cours du mélange des compositions dans l'extrudeuse. Les différentes quantités de mélange-maîtres respectifs dans les compositions 1 à 3 sont détaillées dans le tableau 1. Les teneurs en composés latents, en sel de dibutyle étain et en photosensibilisateur pour les compositions 1 à 3 sont également indiquées dans le tableau 1.Then, these different masterbatches are added by the hopper of an extruder into a mixture of EVS or grafted LLDPE-silane according to the compositions referenced in Table 1. The temperature profile of the extruder allows the polymer blend got to be in the melted state. Temperature The maximum profile is furthermore lower than the release temperature of the crosslinking catalyst of the latent compounds (compositions 1 and 2). More particularly, the temperature profile of the extruder is as follows: 120 ° C - 150 ° C - 160 ° C, with an extrusion head temperature of 170 ° C. At 170 ° C., the thermal stability of the latent compounds PAG and PBL is sufficient not to release their respective crosslinking catalyst during the mixing of the compositions in the extruder. The respective amounts of masterbatch in compositions 1 to 3 are detailed in Table 1. The contents of latent compounds, dibutyltin salt and photosensitizer for compositions 1 to 3 are also shown in Table 1.

Extrusion des compositions et irradiation UVExtrusion of the compositions and UV irradiation

L'étape d'extrusion des différentes compositions 1 à 3 est réalisée à la vitesse de 10m/mn, en déposant une épaisseur de 300µm de ladite composition extrudée autour d'un fil conducteur de cuivre de 0,85mm2 de section transversale.The extrusion step of the various compositions 1 to 3 is carried out at a speed of 10 m / min, by depositing a thickness of 300 .mu.m of said extruded composition around a copper conductor wire of 0.85 mm 2 of cross section.

Puis, uniquement pour les compositions comprenant un composé latent, le fil isolé obtenu est immédiatement irradié par un rayonnement UV (premier traitement UV), d'une longueur d'onde comprise entre 150 et 550 nm, à température ambiante, à l'aide d'un four de type HP6 commercialisé par la société FUSION UV SYSTEMS équipé d'une ampoule à vapeur de mercure moyenne pression de type « D » d'une puissance de 200W/cm et d'un module de réflecteur arrière. Afin d'améliorer l'efficacité du catalyseur provenant du composé latent, une étape de post-traitement UV peut être nécessaire. Celle-ci peut être réalisée sur le fil isolé à température ambiante consécutivement à l'étape d'extrusion. Dans le cadre des exemples décrits, le post-traitement UV consiste à passer le fil isolé 10 fois à 10m/mn dans le four UV.Then, only for the compositions comprising a latent compound, the isolated yarn obtained is immediately irradiated with UV radiation (first UV treatment), with a wavelength of between 150 and 550 nm, at room temperature, using an HP6 type furnace sold by the company FUSION UV SYSTEMS equipped with a medium-pressure mercury vapor lamp type "D" with a power of 200 W / cm and a rear reflector module. In order to improve the efficiency of the catalyst from the latent compound, a UV post-treatment step may be necessary. This can be performed on the insulated wire at room temperature subsequent to the extrusion step. In the context of the examples described, the post-treatment UV consists in passing the insulated wire 10 times at 10m / min in the UV oven.

Les compositions ayant subi un premier traitement UV, et éventuellement un post-traitement UV, sont indiquées dans le tableau 2 ci-après.The compositions having undergone a first UV treatment, and possibly a UV post-treatment, are indicated in Table 2 below.

Bien entendu, augmenter le nombre de lampes ainsi que leur puissance peuvent permettre de ne pas effectuer de post-traitement UV. Le nombre de lampes ainsi que leur puissance pourront être facilement choisis par l'homme du métier pour obtenir une réticulation optimale en fonction de la durée de l'irradiation et de l'épaisseur de la composition à irradier.Of course, increasing the number of lamps as well as their power can make it possible not to carry out UV post-treatment. The number of lamps and their power can be easily selected by the skilled person to obtain optimal crosslinking depending on the duration of the irradiation and the thickness of the composition to be irradiated.

Réticulation des compositions extrudéesCrosslinking of extruded compositions

Les conditions de réticulation sont indiquées dans le tableau 2 ci-après. Elles sont de deux types :

  • réticulation dite « forcée » dans les conditions d'un sauna, à savoir pendant 48h, à 80°C et avec 100% d'humidité relative, et
  • réticulation dite « non forcée » dans des conditions d'auto-réticulation, à savoir pendant 2 jours, à 25°C et avec 50% d'humidité relative.
The crosslinking conditions are shown in Table 2 below. They are of two types:
  • so-called "forced" crosslinking under the conditions of a sauna, namely for 48 hours, at 80 ° C. and with 100% relative humidity, and
  • so-called "non-forced" crosslinking under self-crosslinking conditions, ie for 2 days, at 25 ° C and with 50% relative humidity.

Caractérisation du degré de réticulationCharacterization of the degree of crosslinking

Une fois les compositions extrudées ayant subi les conditions d'un sauna ou les conditions d'auto-réticulation (voir tableau 2), le degré de réticulation est caractérisé selon des méthodes bien connues de l'homme du métier.Once the extruded compositions have undergone the conditions of a sauna or the conditions of self-crosslinking (see Table 2), the degree of crosslinking is characterized according to methods well known to those skilled in the art.

Pour les compositions chargées 1, 2 et 3, la méthode choisie est celle de la mesure du fluage à chaud sous charge.For the charged compositions 1, 2 and 3, the method chosen is that of the measurement of the hot creep under load.

Fluage à chaud sous chargeHot creep under load

La norme NF EN 60811-2-1 décrit la mesure du fluage à chaud d'un matériau sous charge. Le test correspondant est communément désigné par l'anglicisme Hot Set Test.The standard NF EN 60811-2-1 describes the measurement of the hot flow of a material under load. The corresponding test is commonly referred to as the Anglicism Hot Set Test.

Il consiste concrètement à lester une extrémité d'une éprouvette de matériau avec une masse correspondant à l'application d'une contrainte équivalente à 0,2MPa, et à placer l'ensemble dans une étuve chauffée à 200+/-1°C pendant une durée de 15 minutes. Au terme de ce délai, on relève l'allongement à chaud sous charge de l'éprouvette, exprimé en %. La masse suspendue est alors retirée, et l'éprouvette est maintenue dans l'étuve pendant 5 nouvelles minutes. L'allongement permanent restant, également appelé rémanence, est alors mesuré avant d'être exprimé en %.It concretely consists of ballasting one end of a test piece of material with a mass corresponding to the application of a stress equivalent to 0.2 MPa, and placing the assembly in an oven heated to 200 +/- 1 ° C. a duration of 15 minutes. At the end of this period, the hot elongation under load of the test piece, expressed in%, is recorded. The suspended mass is then removed, and the test piece is kept in the oven for another 5 minutes. The remaining permanent elongation, also called remanence, is then measured before being expressed in%.

On rappelle que plus un matériau est réticulé, plus les valeurs d'allongement et de rémanence seront faibles. On précise par ailleurs que dans le cas où une éprouvette viendrait à se rompre en cours d'essai, sous l'action conjuguée de la contrainte mécanique et de la température, le résultat au test serait alors logiquement considéré comme un échec.It is recalled that the more a material is crosslinked, the longer the values of elongation and remanence will be low. It is also specified that in the case where a test piece breaks during the test, under the combined action of the mechanical stress and the temperature, the test result would then logically be considered a failure.

Le tableau 2 reprend les résultats des fluages à chaud obtenus sur les échantillons considérés. Tableau 2 Composition Traitement UV (premier traitement UV) Post-traitement UV Conditions de réticulation Fluage à chaud Allongement sous charge (%) Rémanence (%) 1 OUI OUI AUTO-RETICULATION 95 25 OUI OUI SAUNA 75 15 2 OUI OUI AUTO-RETICULATION 40 5 OUI OUI SAUNA 30 0 3 NON NON AUTO-RETICULATION ECHEC ECHEC Table 2 shows the results of hot flowing obtained on the samples considered. <b><u> Table 2 </ u></b> Composition UV treatment (first UV treatment) UV post-treatment Crosslinking conditions Hot creep Lengthening under load (%) Remanence (%) 1 YES YES SELF-CURE 95 25 YES YES SAUNA 75 15 2 YES YES SELF-CURE 40 5 YES YES SAUNA 30 0 3 NO NO SELF-CURE FAILURE FAILURE

Pour les compositions chargées, à savoir la composition 1 (EVS + Mg(OH)2 + PBL) et la composition 2 (LLDPE-greffé silane + Mg(OH)2 + PBL), la réticulation par PBL s'avère particulièrement efficace, ce que montrent les faibles valeurs d'allongement et de rémanence (fluage à 200°C). Le post-traitement UV permet en outre d'améliorer efficacement la réticulation.For the charged compositions, namely composition 1 (EVS + Mg (OH) 2 + PBL) and composition 2 (LLDPE-grafted silane + Mg (OH) 2 + PBL), the crosslinking by PBL proves to be particularly effective, as shown by the low elongation and persistence values (creep at 200 ° C). The UV post-treatment also makes it possible to improve the crosslinking effectively.

Enfin, les compositions chargées 1 et 2, après post-traitement UV, sont auto-réticulantes, contrairement à la composition chargée 3 (comparée à la composition chargée 2) où l'auto-réticulation ne se fait pas après 48 heures, voire même après plusieurs dizaines de jours. On note ainsi un effet bénéfique du catalyseur de réticulation latent (PAG PBL) par rapport au sel d'étain (DBTm) qui se répercute non seulement sur la toxicité du mélange ainsi obtenu, mais aussi sur les conditions de réticulation du mélange.Finally, the charged compositions 1 and 2, after UV post-treatment, are self-crosslinking, unlike the charged composition 3 (compared to the charged composition 2) where the self-crosslinking is not done after 48 hours, or even after several dozens of days. There is thus a beneficial effect of the latent crosslinking catalyst (PAG PBL) with respect to the tin salt (DBTm) which has repercussions not only on the toxicity of the mixture thus obtained, but also on the crosslinking conditions of the mixture.

Claims (17)

  1. A cross-linkable composition comprising:
    - an olefin polymer including on its main chain hydrolyzable sliane groups, and
    - a latent compound capable of releasing a cross-linking catalyst under the action of a rise in temperature and/or actinic radiation, said cross-linking catalyst being a catalyst for hydrolysis and condensation of silanol functions,
    characterized in that the latent compound is a compound capable of releasing a base as a cross-linking catalyst.
  2. The composition according to claim 1, characterized in that the olefin polymer is an ethylene polymer.
  3. The composition according to claim 1 or 2, characterized in that the hydrolyzable silane groups are alkoxysilane groups and/or carboxysilane groups.
  4. The composition according to any of the preceding claims, characterized in that the content of the latent compound in the composition is from 50 to 50,000 ppm.
  5. The composition according to any of claims 1 to 4, characterized in that the latent compound is an ionic compound capable of releasing a base as a cross-linking catalyst.
  6. The composition according to claim 5, characterized in that the latent compound is a tertiary amine.
  7. The composition according to claim 5 or 6, characterized in that the latent compound is selected from ammonium salts of alpha-ketocarboxylic acids; the ammonium salts of carboxylic acids bearing an aromatic group; N-(benzophenonylmethyl)-tri-N-alkyl-ammonium triphenylalkylborate salts; benzhydrylammonium salts; and trialkylfluorenylammonium iodides; or one of their mixtures.
  8. The composition according to any of claims 1 to 4, characterized in that the latent compound is a non-ionic compound capable of releasing a base as a cross-linking catalyst.
  9. The composition according to claim 8, characterized in that the base is a tertiary amine.
  10. The composition according to claim 9, characterized in that the tertiary amine is selected from diazabicyclo-octanes; N-alkyl-morpholines; tetramethylguanidines (TMG); diazabicyclononenes (DBN); diazabicyclo-undecenes (DBU).
  11. The composition according to claim 9 or 10, characterized in that the latent compound is selected from diazabicyclononanes; and diazabicyclo-undecanes.
  12. The composition according to claim 9, characterized in that the latent compound is selected from 4-(methylthiobenzoyl)-1morpholinoethane; and (4-morpholinobenzoyl)-1-benzyl-1-dimethylaminopropane.
  13. A method for making a cross-linked article comprising the steps of:
    i. heating the composition as defined in claims 1 to 12 in order to release the cross-linking catalyst from the latent compound, and
    iii. cross-linking the composition obtained in step i.
  14. The method according to claim 13, characterized in that the heating step i is carried out at the extrusion head of an extruder or after extrusion of the composition.
  15. A method for making a cross linked article comprising the steps of:
    ii. exposing the composition as defined in claims 1 to 12, to actinic radiation in order to release the cross-linking catalyst from the latent compound, and
    iii. cross-linking the composition obtained in step ii.
  16. The method according to claim 15, characterized in that step ii for exposure to actinic radiation is carried out under radiation having a wavelength ranging from 185 nm to 400 nm.
  17. The method according to claim 15 or 16, characterized in that the exposure step ii is carried out after extrusion of the composition.
EP09177715A 2008-12-22 2009-12-02 Crosslinkable composition comprising a silane grafted polymer and a latent compound Not-in-force EP2199310B1 (en)

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EP2562768B1 (en) * 2011-08-26 2014-04-23 Borealis AG Cable comprising a silane crosslinkable polymer composition
EP2562209B1 (en) * 2011-08-26 2020-04-01 Borealis AG Silane crosslinkable polymer composition
WO2013142956A1 (en) * 2012-03-28 2013-10-03 Uti Limited Partnership Methods and compounds for photo lewis acid generation and uses thereof
CN110607020B (en) * 2019-09-20 2020-11-06 江苏德威新材料股份有限公司 UVLED light attenuation irradiation resistant crosslinked polyethylene insulating material and preparation method thereof

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BE794718Q (en) 1968-12-20 1973-05-16 Dow Corning Ltd OLEFINS CROSS-LINKING PROCESS
US4101513A (en) * 1977-02-02 1978-07-18 Minnesota Mining And Manufacturing Company Catalyst for condensation of hydrolyzable silanes and storage stable compositions thereof
US5047476A (en) * 1989-05-12 1991-09-10 Union Carbide Chemicals And Plastics Company Inc. Process for crosslinking hydrolyzable copolymers
JP2886007B2 (en) * 1992-10-23 1999-04-26 鐘淵化学工業株式会社 Curable composition for paint
DE69422755D1 (en) * 1993-07-22 2000-03-02 Kanegafuchi Chemical Ind Curable composition
US6362301B1 (en) * 1994-06-13 2002-03-26 Rohm And Haas Company Curable composition
WO1998018873A1 (en) * 1996-10-31 1998-05-07 Kaneka Corporation Curable composition for top coating and articles coated therewith
DE69815073T3 (en) * 1997-03-14 2008-07-03 Minnesota Mining And Manufacturing Co., St. Paul ON-REQUEST HARDENING OF MOISTURE-REPRODUCTIVE COMPOSITIONS WITH REACTIVE FUNCTIONAL SILANE GROUPS
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